Journal of Natural Gas Science and Engineering 31 (2016) 747e757

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Journal of Natural Gas Science and Engineering

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Kinetic modeling and optimization of Claus reaction furnace

Samane Zarei, Hamid Ganji*, Maryam Sadi, Mehdi Rashidzadeh
Research Institute of Petroleum Industry (RIPI), Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Optimization of Claus sulfur recovery plants requires a reliable kinetic model to describe the reaction
Received 23 December 2015 furnace and waste heat boiler. In order to develop a suitable kinetic model for prediction of reaction
Received in revised form furnace and waste heat boiler effluents, several reaction schemes were tested and the best reaction set
5 March 2016
was selected. The kinetic parameters of the best reaction scheme were optimized and different reactor
Accepted 29 March 2016
networks were analyzed using the optimum reaction set. The modified model results were in good
Available online 31 March 2016
agreement with the experimental measured plant data both before and after waste heat boiler (The
mean absolute errors were 7.62% and 7.88% respectively). In addition, the effects of increasing ammonia
Keywords:
Claus process
and oxygen content of feed, and air to acid gas ratio on reaction furnace effluents were investigated
Reaction furnace through various case studies. An optimization study was performed to control the operating variables of
Waste heat boiler an operating sulfur recovery unit in order to obtain optimum conditions (including maximum reaction
Modeling furnace temperature), maintain H2S to SO2 ratio at constant 2 and lower COS emissions from waste heat
Optimization boiler.
Kinetic © 2016 Elsevier B.V. All rights reserved.

1. Introduction
Environmental regulations have become more stringent on
sulfur dioxide emissions to atmosphere. One of the main strategies
of reducing sulfur emissions is to increase the performance of the
sulfur recovery units (SRU). The modified Claus process is one of the
major processes which converts toxic hydrogen sulfide to
elemental sulfur from acid gas during sour natural gas processing
and refinery upgrading (Dowling et al., 1995). The modified Claus
process in which hydrogen sulfide is converted to sulfur can be
depicted by the following simple overall reaction:
H2S þ 0.5O2 / 0.5S2 þ H2O
The sulfur recovery in the modified Claus process is obtained via
the two reaction steps including thermal and catalytic steps. The
first step is a thermal step where one third of hydrogen sulfide
(H2S) is partially oxidized and sulfur dioxide (SO2) is produced at
very high temperatures.
H2S þ 1.5O2 / SO2 þ H2O
* Corresponding author.
E-mail address: ganjih@ripi.ir (H. Ganji).
The second step involves the reaction between the un-reacted
hydrogen sulfide and sulfur dioxide over a catalytic bed at lower
temperatures:
2H2S þ SO2 4 1.5S2 þ 2H2O (3)
Conversion of H2S to SO2 in the modified Claus process is con-
ducted in the reaction furnace (RF) which is a refractory lined cy-
lindrical vessel. Acid gas stream at a pressure typically ranging from
130 to 180 kPa is fed to the reaction furnace burner along with an
appropriate quantity of air to oxidize feed contaminates and results
in a 2:1 ratio of H2S:SO2 in the reactor effluent. The combustion of
(1) acid gases in the RF is performed at temperature ranges of
975e1300  C and gas residence times 0.5e2.0 s (Monnery et al.,
1993).
Since the combustion process in the RF provides substantial
sulfur recovery and affects the entire plant emissions, any modifi-
cation in the RF affects sulfur conversion and emissions from Claus
plant (Monnery et al., 1993). Therefore any improvement in the
reaction furnace has direct impact on reduction of sulfur emissions
(2) to the atmosphere.
The waste heat boiler (WHB) which is a following equipment
after the RF cools the combusted products of the RF from
926e1300  C to about 230e370  C in one or two tube passes pro-
ducing steam on the shell side (Monnery et al., 1993).
Optimization of the modified Claus process for further sulfur

http://dx.doi.org/10.1016/j.jngse.2016.03.086
1875-5100/© 2016 Elsevier B.V. All rights reserved.
748 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757
recovery and lower emissions requires knowledge of reaction ki-
netics of numerous reactions occurring in the RF and WHB (Karan,
1998). However, the available models do not consider the kinetic
limitations of various side reactions in the RF and WHB. These
models can not properly predict CO, H2, COS and CS2 concentrations
(Karan et al., 1999a).
Although several researchers have investigated the modeling of
the Claus plant or specific unit operations of the Claus process
(Bennett and Meisen, 1973; Jones et al., 2012; Karan et al., 1999b;
Khudenko et al., 1993; Manenti et al., 2012a, 2013b; Monnery
et al., 1993; Nasato, 1993; Nasato et al., 1994; ZareNezhad and
Hosseinpour, 2008), but most of these modeling works have used
restricted equilibrium models to estimate product distribution
from the Claus reaction furnace (Bennett and Meisen, 1973;
Khudenko et al., 1993; Monnery et al., 1993; ZareNezhad and
Hosseinpour, 2008). Bennett and Meisen (1973) considered 36
chemical species including many nitrogen compounds and radicals,
and reported equilibrium calculations in H2S-Air system up to a
temperature 2000 K.
Khudenko et al. (1993) have computed the equilibria of Claus
reaction furnace under oxygen enrichment conditions employing
Gibbs energy minimization method and concluded that oxygen-
based Claus process can be used for reducing the equipment size.
Monnery et al. (1993) applied the various methods such as the
Gibbs energy minimization method, Fisher monograph and west-
ern research correlations in order to estimate the reaction furnace
effluents and concluded that results of these various methods are
not in agreement with plant data taken both after and before the
waste heat boiler. Selim et al. (2008) investigated critical roles of
gases accompanied with the H2S in the sulfur recovery process on
determining the optimum operating temperature to obtain the
maximum sulfur recovery. ZareNezhad and Hosseinpour (2008)
applied chemical equilibrium calculation in order to investigate
application of different alternatives for increasing the RF temper-
ature of Claus units. Some researchers have investigated the effects
of acid gas feed composition on Claus process experimentally
(Ibrahim et al., 2013, 2014; Selim et al., 2011, 2012a, 2012b, 2013,
2014).
Nasato et al. (1994) developed a rigorous one dimensional
model of the WHB tube with a reaction set composed of H2S
decomposition and COS formation reactions. In the next work by
Karan et al. (1994), radiation heat transfer was considered in the
reaction quenching of the waste heat boiler. It was the main dif-
ference between two studies (Karan et al., 1994; Nasato et al., 1994)
and enhanced performance of the model in prediction of gas ef-
fluents. Karan et al. (1999b) used of new kinetic rate expression for
COS decomposition to model WHB whose absolute average de-
viations for COS concentrations was in 5e13%.In addition, only the
WHB was modeled and the feed composition and other properties
were obtained from the Sames et al. (1991).
The other works in case of the kinetic modeling are based on a
detailed kinetic scheme for prediction of the Claus reaction furnace
effluents (Manenti et al., 2013a, 2013b, 2012b; Pierucci et al., 2004;
Scho€ neberger et al., 2007). Pierucci et al. (2004) modeled the
thermal reactor with a detailed kinetic scheme based on a radical
approach including 130 species and more than 1500 elementary
reactions.
Manenti et al. (2013b) used a kinetic model consist of 146 spe-
cies and 2412 reactions to model sulfur recovery unit thermal stage
including the RF and the WHB. Their model was validated on the
industrial data of sulfur recovery units operating in the Nanjing and
Mumbai plants. In an another research, Manenti et al. (2013a) used
a kinetic model with 2400 reactions and 140 species in a proper
reactor network to optimize elemental sulfur recovery and steam
generation. Manenti et al. (2014) utilized this kinetic scheme and
carried out an integrated process-energy optimization at the total
plant scale (2014). Javanmardi and Fatemi (2015) modeled a sulfur
recovery unit based on straight through sour natural gas with two
different approaches of equilibrium and kinetic methods. They
concluded that the kinetic model has more accurate results than
equilibrium model.
Jones et al. (2012) identified a reaction set including indepen-
dent reactions and used a four stage method to describe the
product distribution of measured WHB effluents. After modeling of
Claus plant using the developed reaction sets, two optimization
studies were carried out. These studies showed that there exists an
optimal steam pressure and H2S/SO2 ratio that balances hydrogen
yield, oxygen demand, and power generation. Jones et al. (2012) did
not compare calculated RF outlet with measured experimental data
at this equipment and their comparison was limited to the waste
heat boiler effluents.
In this study, reaction furnace and waste heat boiler were
modeled both separately and incorporated via two different reac-
tion schemes consisting same rate expressions. For this purpose,
different reaction schemes were examined as to their efficiencies in
predicting reaction furnace emissions; the reaction scheme with
fewer errors was then chosen. To reach a higher accuracy, different
reactor networks were tested and fitting kinetic parameter
methods were employed.
The main difference between the present study and that of Jones
et al. (2012) is the reaction schemes applied in modeling the re-
action furnace and the waste heat boiler. Jones et al. (2012)
considered a reaction scheme, added other reactions and fitted
their kinetic parameters using the waste heat boiler effluents in
order to reach a higher accuracy while in the present research, the
kinetic parameters of the chosen reaction scheme were fitted in
agreement with the reaction furnace and waste heat boiler efflu-
ents. After modeling the reaction furnace and waste heat boiler
with sufficient errors, case studies were conducted so as to inves-
tigate the influence of ammonia and oxygen increments in acid gas
feed and air to acid gas molar flow ratio on product distribution and
the temperature of the reaction furnace. In addition, one optimi-
zation study was done to determine the values of reaction furnace
feed temperature, steam pressure and the air to acid gas molar flow
ratio in order to further optimize the reaction furnace temperature,
carbonyl sulfide emission, sulfur production and H2S to SO2 ratio.
2. Plant data
In this work, the parameters and data were obtained from the
Ultramar Refinery Field (Sames et al., 1991). Sames et al. (1991)
measured the plant data by sampling directly from the rear
chamber of the reaction furnace using high quench rates. Tests
were done at various oxygen enrichment levels, feed compositions
and residence times. Such data were the only available measured
data at the reaction furnace outlet. The specific objective of their
study was to measure the quantity of species at the reaction furnace
and then to determine the degree of reaction occurring in the waste
heat boiler. In this regard, measured quantities of compounds at the
waste heat boiler outlet were also reported. Details of feed stream
compositions, test conditions, product distribution both prior to
and following the waste heat boiler are given in Sames et al. (1991).
3. Model
The reaction furnace is composed of two zones, namely the
flame or oxygen rich zone and post flame or anoxic zone. The flame
zone is an oxygen consuming zone and its temperature exceeds
2000  C. Whereas residence time of the flame zone is very short
and in order of milliseconds, residence time in the oxygen deficient
 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757 749

post flame zone may range from 0.5 to 2.0 s depending on the flow following ordinary differential equations including mass and en-
rate and temperature (Chin et al., 2001). Thus, it seems that ergy balance equations and actual mean residence time should be
different reactor networks such as a combination of CSTR and PFR solved.
reactors in series and parallel modes would model these two zones
of RF. The WHB is made of one or two tube passes with anoxic zone dFj X
nature where hot gases from RF are cooled down to 250e300  C.
¼A yij rij j ¼ 1; …; nc i ¼ 1; …; nR (5)
dz i
Supposing negligible radial concentration and temperature gradi-
ents, one dimensional plug flow assumption can be applied in the
dT X X
RF and WHB modeling. Due to the completely different natures of ¼A hj yij rij (6)
these equipments, i.e. RF and WHB, different reaction schemes dz j i
were made use of in their modeling.
The literature reports a wide number of possible reactions for 0 11
the RF, most of which are oxidation reactions (Monnery et al., 1993). dtR 1 @
X
Table 1 shows the candidate reactions list reported in the literature ¼ ðAPÞðRTÞ Fj A (7)
dz j
for complete description of the RF. As seen in Table 1, for certain
reactions, more than one reaction rate expression is given because Above equations can be rearranged and the mass and energy
of such different experimental conditions as temperature, pressure balance equations can be written based on residence time as
and reactor type. In the present work, apart from the reactor type, follow:
we specified un-catalytic gas phase rate expressions at high tem-
peratures. It is possible to select the best kinetic expression by
P
RT Fj
examining it in a suitable model. Accordingly, about 168,000 re- dFj j X
¼ yij rij j ¼ 1; …; nc i ¼ 1; …; nR (8)
action schemes were considered and in certain cases presence or dtR P i
absence of a specific reaction was further investigated. The proce-
dure of selecting reaction schemes is as follows. P
Based on Table 1, eight rate expressions have been reported for RT Fj
dT j X X
H2S decomposition reaction. Therefore we have nine alternatives ¼ hj yij rij (9)
dtR P
for this reaction including 8 rate expressions for H2S decomposition j i
and a choice for occurrence of this reaction. With a same procedure,
The above ordinary differential equations were solved by Run-
the total choices of 4 is obtained for the COS recombination reac-
geeKutta order 4 and the numerical algorithm was written in
tion. This procedure was repeated for other reactions in Table 1 but
MATLAB programming software.
for combustion reactions, absence of reactions has not been
The investigation of model results obtained from different re-
considered in calculations as these combustion reactions certainly
action sets indicated that the reaction set of Table 2 was the best
occur in the RF. Therefore total number of possible reaction
possible reaction scheme that could be employed in modeling the
schemes is calculated from multiplication of all reaction alterna-
reaction furnace effluents. It must be noticed that equilibrium
tives as follows:
constants in Table 2 were calculated using 7 coefficient NASA
polynomials whose coefficients were obtained from NASA data
Total number of reaction Schemes ¼ 9  4  6  …  1 (4)
bank (McBride et al., 1993).
The reaction furnace was modeled using different reaction Table 3 compares the calculated reaction furnace effluents with
schemes assuming adiabatic plug flow reactor. Considering adia- the measured experimental data. The mean absolute percentage
batic plug flow assumption and negligible pressure drop, the error (MAPE) of each compound and temperature is also given in

Table 1
Candidate list of reactions in the reaction furnace

Reaction Reference

H2S 4 H2 þ S2
CO þ 0.5S2 4 COS
CO2 þ H2 4 CO þ H2O
CO þ H2S 4 COS þ H2
H2S þ 0.5SO2 4 H2O þ 0.75S2
CO2 4 CO þ 0.5O2
H2O 4 H2 þ 0.5O2
CH4 þ 1.5O2 / CO þ 2H2O
CH4 þ 0.5O2 / CO þ 2H2
CH4 þ H2O / CO þ 3H2
H2S þ 1.5O2 / SO2 þ H2O
NH3 / 0.5N2 þ 1.5H2
NH3 þ 0.75O2 / 0.5N2 þ 1.5H2O (Monnery et al., 2001)
C2H4 þ 2O2 / 2CO þ 2H2O
C2H6 þ 2.5O2 / 2CO þ 3H2O
C3H8 þ 3.5O2 / 3CO þ 4H2O
C4H10 þ 4.5O2 / 4CO þ 5H2O
(Adesina et al., 1995; Chin, 2000; Dowling and Clark, 1999; Dowling et al., 1990; Harvey et al., 1998; Hawboldt et al., 2000; Kaloidas and
Papayannakos, 1989; Karan et al., 1999c)
(Karan et al., 1998; Karan et al., 1999a; Klemm and Davis, 1974)
(Bustamante et al., 2005; Graven and Long, 1954; Jones and Lindstedt, 1988; Karan, 1998; Tingey, 1966)
(Karan et al., 1999a)
(Monnery et al., 2000; Tesner et al., 1990)
(Dryer and Glassman, 1973; Williams et al., 1969)
(Jones and Lindstedt, 1988; Peters, 1979)
(Dryer and Glassman, 1973; Westbrook and Dryer, 1981; Williams et al., 1969)
(Jones and Lindstedt, 1988; Westbrook and Dryer, 1981)
(Jones and Lindstedt, 1988)
(Monnery et al., 2000)
(Monnery et al., 2001)
(Westbrook and Dryer, 1981)
(Westbrook and Dryer, 1981)
(Westbrook and Dryer, 1981)
(Westbrook and Dryer, 1981)
750 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757

Table 2
Reaction rate expressions of the chosen kinetic scheme

Reaction Rate Expression Reference

       
H2S 4 H2 þ S2 (Dowling et al., 1990)
rH2 mmol
3 sec ¼ 4:3  106 exp  RT
26 kcal
mol
CH2 PS2 ðatmÞ  3:6  108 exp  RT
48 kcal
mol
CH2 S
   
CO þ 0.5S2 4 COS 0 1 0 1 (Karan et al., 1998)
  kJ
55:8 mol kJ
180 mol
rCO mkmol
3 sec ¼ 3:18  105 exp@  RT
ACCO CS  4:36  109 exp@ 
2 RT
ACCOS Ctotal

     !
CO2 þ H2 4 CO þ H2O CCO CH2 O (Karan, 1998)
kmol kJ
rCO2 m3 sec
¼ 8:59  1010 exp  270:5
RT mol
CCO2 CH0:5
2
 K1eq CH0:5
2

CO þ H2S 4 COS þ H2     " #

(Karan et al., 1999a)
rCO kmol ¼ 1:59  105 exp  110:91 kJ
C C 0:5  CCOS CH2
m3 sec RT mol CO H2 S C 0:5
K eq
H2 S
       
H2S þ 0.5SO2 4 H2O þ 0.75S2 (Tesner et al., 1990)
rH2 S mol
m3 sec
¼ 3:18  106 exp 14:3 RT
kcal
mol
CH2 S CSO0:5  31081 exp 8:5 kcal
2 RT mol
CH2 O CS0:75
2
   
CH4 þ 1.5O2 / CO þ 2H2O (Dryer and Glassman, 1973)
rCH4 cmmol3 sec ¼ 1013:2 exp  48:4 kcal C 0:7 C 0:8
RT mol CH4 O2
    
H2S þ 1.5O2 / SO2 þ H2O mol 11 kcal (Monnery et al., 2000)
rH2 S cm3 sec ¼ 14 exp RT mol PH2 S ðatmÞPO1:5 2
    
NH3 / 0.5N2 þ 1.5H2 16:5 (Monnery et al., 2001)
rNH3 cm3 sec ¼ 0:00842 exp RT
mol kcal
mol
PNH3 ðatmÞ
1:25

   
C2H4 þ 2O2 / 2CO þ 2H2O (Westbrook and Dryer, 1981)
rC2 H4 cmmol
3 sec ¼ 2:4  1012 exp  RT 30 kcal C 0:1 C 1:65
mol C2 H4 O2
   
C2H6 þ 2.5O2 / 2CO þ 3H2O (Westbrook and Dryer, 1981)
rC2 H6 cm3 sec ¼ 1:3  10 exp  RT mol CC0:1
mol 12 30 kcal
2 H6
CO1:65
2
   
C3H8 þ 3.5O2 / 3CO þ 4H2O (Westbrook and Dryer, 1981)
rC3 H8 cmmol
3 sec ¼ 1  1012 exp  RT 30 kcal C 0:1 C 1:65
mol C3 H8 O2
   
C4H10 þ 4.5O2 / 4CO þ 5H2O (Westbrook and Dryer, 1981)
rC4 H10 cmmol
3 sec ¼ 8:8  10 11 exp  30 kcal C 0:1 C 1:65
RT mol C4 H10 O2

Table 3
A comparison between the calculated and experimental data at the reaction furnace outlet

H2 N2 CO CO2 H2S COS SO2 H2O S2 Ar Tout(K)

Test1 Experimental 10.04 132.59 2.74 6.43 10.31 0.47 5.67 95.30 33.86 1.52 1594.15
Calculated 9.91 134.41 2.79 7.61 12.48 0.12 5.80 93.79 33.11 1.55 1730.27
Test2 Experimental 7.94 144.37 2.07 5.88 9.66 0.29 4.30 82.78 28.97 1.68 1497.15
Calculated 7.40 149.44 1.92 6.85 11.07 0.11 5.34 81.94 27.79 1.74 1639.81
Test3 Experimental 3.86 87.62 1.32 4.80 6.37 0.24 3.28 45.60 20.96 1.05 1481.15
Calculated 3.43 85.99 1.18 5.28 8.04 0.12 2.81 44.56 20.48 1.03 1590.80
Test4 Experimental 5.78 91.42 2.07 6.34 9.82 0.42 4.11 61.47 28.91 1.10 1558.15
Calculated 5.68 94.87 2.12 7.00 10.04 0.14 4.11 61.90 29.04 1.13 1689.60
Test5 Experimental 11.18 111.75 3.52 6.60 11.52 0.60 6.17 121.40 40.02 1.26 1761.15
Calculated 14.84 113.88 4.07 8.00 13.34 0.10 7.47 117.52 38.79 1.28 1874.85
Mean Absolute 10.73 2.48 7.50 15.28 15.95 67.28 12.35 1.76 2.43 2.32 8.07
Percentage Error

this table. As can be seen, except for carbonyl sulfide which has a
significant error, the model has reasonable precision in predicting
the molar flow of other compounds. To improve the model and kf C C
rCO ¼ 0 / ¼ COS total (11)
reduce its error, different reactor networks were analyzed and ki- kb CCO CS2
netic parameter fitting methods were made use of.
On the other hand for COS recombination equilibrium reaction,
A minute review of Table 2 shows that the reaction rate ex-
the equilibrium constant is given by:
pressions related to hydrogen sulfide and carbonyl sulfide decom-
position are not thermodynamically consistent. For equilibrium
reactions, the ratio of forward to backward rate constant (kf/kb) CCOS
equals to equilibrium constant which should be only a function of K¼ (12)
CCO CS0:5
temperature. In thermodynamically inconsistence rate expression, 2

this ratio is a function of concentration or partial pressure of spe- With replacing Equation (11) in Equation (12), we have:
cific component or total concentration and pressure of the system
(Hawboldt et al., 2000).
Based on Table 2, the rate expression of COS recombination is as 0:5
kf CS2
follows: K¼ (13)
kb Ctotal
As it can be seen, the equilibrium constant is a function of
rCO ¼ kf CCO CS2  kb CCOS Ctotal (10) concentration and it is impossible for a consistent reaction.
Therefore the mentioned rate expressions were replaced with their
Where kf and kb are forward and backward rate constants, thermodynamically consistent rate expression forms from Dowling
respectively. Under equilibrium condition: and Clark (1999) and Karan et al. (1999a) as follows:
 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757 751

     Claus reaction; their kinetic parameters were further fitted using

mol 6 131:3 kJ the reaction furnace and waste heat boiler inlet and outlet data.
rH2 ¼ 3:46  10 exp  CH2 CS2
m3 sec RT mol In waste heat boiler, Karan et al. (1994) considered the details of
  
216:6 kJ material, energy and momentum balance equations. The reaction
 2:26  109 exp  CH2 S CS0:5 scheme employed in modeling the waste heat boiler was composed
RT mol 2

of the thermal decomposition of carbonyl sulfide and hydrogen

(14)
sulfide as previous works in this field (Karan et al., 1994, 1999b;
  Nasato et al., 1994). In other word, Equations (14 and 15) were
0 kJ 1 used in the waste heat boiler modeling of this research.
  55:8 mol 
kmol The main reason why the waste heat boiler was considered in
rCO ¼ 3:18  10 exp@
5 A CCO CS
m3 sec RT 2
the adjusting work was because thermal decomposition reactions
 were in accordance with Equations (14 and 15). It is known that
1
 C C 0:5 high temperature in the reaction furnace overcomes the decom-
Keq COS S2 position reaction while low temperature in the waste heat boiler
(15) allows for a recombination reaction. Therefore, introducing one
rate expressions that can be applied to both the reaction furnace
The backward activation energy and pre exponential factor of
and waste heat boiler modeling meant that both equipments had to
rate constants of Equation (15) were obtained using 7 coefficient
be taken into consideration.
NASA polynomials whose values were 145.09 kJ/mol and
The adjusted kinetic parameters and related reactions are pre-
4.1156  108 (kmol/m3)0.5respectively.Incorporating the above
sented in Table 6. Table 7 compares the reaction furnace calcula-
rate expressions in the reaction scheme increased the MAPE of the
tions with the experimental data. As can be seen, the mean absolute
model from 13.81 to 24.28%. The results of the calculations and
percentage error of each compound ranges from 1.16% for sulfur
MAPE of each compound are presented in Table 4 which shows a
element to 14.13% for hydrogen. The overall mean absolute per-
significant increase in error due to the use of the new thermody-
centage error for concentration significantly dropped from 24.28 to
namically consistent rate expressions in the reaction scheme.
7.62%.
The analysis of the following reactor networks was considered
Tables 8 and 9 draw a comparison between experimentally
as a method of error reduction in the modeling of RF:
measured plant data at the waste heat boiler outlet and model
results at two cases, namely parallel and series. In parallel
1. A single PFR for the description of the flame and anoxic zones of
modeling, the waste heat boiler is modeled separately and inde-
RF.
pendently of reaction furnace using experimental measured data at
2. A single CSTR which its residence time equals that of RF.
the waste heat boiler inlet. In series modeling, however, modeled
3. A combination of CSTR with low residence time in order of
results of reaction furnace are employed as feeds in the waste heat
milliseconds at flame zone and a PFR reactor with RF residence
boiler modeling. Overall mean absolute percentage errors for con-
time for anoxic zone.
centration were 6.25% and 7.88%, respectively. According to Table 8,
4. A combination of CSTR with low residence time at flame zone
MAPEs of compounds range from 0.70 to 15.73% in and from 1.27 to
and another CSTR for the description of anoxic zone with a
14.94% in series modeling.
residence time equal to that of RF.
In this study, the reaction furnace and waste heat boiler
modeled both separately and incorporated using reaction furnace
The MAPE of each compound and the overall MAPEs for con-
and waste heat boiler effluents. The introduced reaction expres-
centration and temperature are presented in Table 5 which in-
sions can be utilized in both the reaction furnace and waste heat
dicates that the single PFR reactor network is suitable for describing
boiler modeling, whereas the results of Jones et al. (2012) were
what actually happens in the reaction furnace. Following the se-
limited to waste heat boiler outlet and effluents of reaction furnace
lection of the best reactor network, the fitting kinetic parameters
were not considered in their work. In other words, Jones et al.
were specified in order to reduce the model error. As is shown in
(2012) can only predict the waste heat boiler effluents while the
Table 4, hydrogen, sulfur dioxide, carbon monoxide and carbonyl
present work can be used in prediction of both the reaction furnace
sulfide have higher errors that have to be reduced by considering
and waste heat boiler outlets.
the most sensitive reactions and fitting their kinetic parameters.
In the study, we considered the reaction of thermal decompo-
sition for carbonyl sulfide and hydrogen sulfide compounds, carbon
monoxide and hydrogen sulfide combination reaction and second

Table 4
Reaction furnace output using thermodynamically consistent rate expressions in comparison to the measured plant data

H2 N2 CO CO2 H2S COS SO2 H2O S2 Ar Tout(K)

Test1 Experimental 10.04 132.59 2.74 6.43 10.31 0.47 5.67 95.30 33.86 1.52 1594.15
Calculated 9.91 134.41 2.79 7.61 12.48 0.12 5.80 93.79 33.11 1.55 1730.27
Test2 Experimental 7.94 144.37 2.07 5.88 9.66 0.29 4.30 82.78 28.97 1.68 1497.15
Calculated 7.40 149.44 1.92 6.85 11.07 0.11 5.34 81.94 27.79 1.74 1639.81
Test3 Experimental 3.86 87.62 1.32 4.80 6.37 0.24 3.28 45.60 20.96 1.05 1481.15
Calculated 3.43 85.99 1.18 5.28 8.04 0.12 2.81 44.56 20.48 1.03 1590.80
Test4 Experimental 5.78 91.42 2.07 6.34 9.82 0.42 4.11 61.47 28.91 1.10 1558.15
Calculated 5.68 94.87 2.12 7.00 10.04 0.14 4.11 61.90 29.04 1.13 1689.60
Test5 Experimental 11.18 111.75 3.52 6.60 11.52 0.60 6.17 121.40 40.02 1.26 1761.15
Calculated 14.84 113.88 4.07 8.00 13.34 0.10 7.47 117.52 38.79 1.28 1874.85
Mean Absolute 56.30 2.46 35.73 3.98 6.96 84.81 42.72 4.79 2.71 2.32 5.77
Percentage Error
752 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757

Table 5
Results of applying different reactor networks

Reactor Network H2 N2 CO CO2 H2S COS SO2 H2O S2 Ar MAPE of MAPE of

Concentration Temperature

PFR 56.30 2.46 35.73 3.98 6.96 84.81 42.72 4.79 2.71 2.32 24.28 5.77
CSTR 77.76 9.48 71.83 26.08 14.80 81.09 37.24 2.12 5.68 9.67 33.58 5.67
CSTR þ PFR 56.75 2.50 36.19 3.98 6.97 84.82 42.89 4.75 2.66 6.50 24.39 5.83
CSTR þ CSTR 77.60 9.43 71.48 25.87 14.67 81.14 37.45 2.06 5.63 9.63 33.49 5.67

Table 6
The adjusted kinetic parameters

Reaction Initial parameter Fitted parameter

k E (kJ/mol) k E (kJ/mol)

COS 4 CO þ 0.5S2 4.1156  108 145.09 6.7780  106 120.18

COS þ H2 4 CO þ H2S 6.0612  106 112.98 1.3611  107 200.13
H2S 4 H2 þ 0.5S2 2.2600  109 216.60 1.8640  109 243.67
H2 þ 0.5S2 4 H2S 3.4600  106 131.30 3.9890  106 154.96
0.75S2 þ H2O / H2S þ 0.5SO2 31,081 8.50 28,426 9.07

Table 7
The Calculated reaction furnace effluents after kinetic parameters optimization in comparison to the measured plant data

H2 N2 CO CO2 H2S COS SO2 H2O S2 Ar Tout(K)

Test1 Experimental 10.04 132.59 2.74 6.43 10.31 0.47 5.67 95.3 33.86 1.52 1594.15
Calculated 9.62 134.41 2.62 7.51 10.98 0.45 4.88 95.65 34.15 1.55 1731.28
Test2 Experimental 7.94 144.37 2.07 5.88 9.66 0.29 4.30 82.78 28.97 1.68 1497.15
Calculated 6.68 149.45 1.71 6.89 9.89 0.34 4.30 83.92 28.78 1.74 1644.44
Test3 Experimental 3.86 87.62 1.32 4.80 6.37 0.24 3.28 45.60 20.96 1.05 1481.15
Calculated 3.34 85.99 1.11 5.19 7.08 0.29 2.32 45.62 21.11 1.03 1590.04
Test4 Experimental 5.78 91.42 2.07 6.34 9.82 0.42 4.11 61.47 28.91 1.10 1558.15
Calculated 5.81 94.87 2.06 6.79 8.67 0.43 3.59 63.15 29.85 1.13 1686.17
Test5 Experimental 11.18 111.75 3.52 6.60 11.52 0.60 6.17 121.40 40.02 1.26 1761.15
Calculated 15.28 113.88 3.99 7.76 11.44 0.52 6.74 119.11 39.90 1.28 1871.09
Mean Absolute 14.13 2.48 10.45 13.35 6.48 11.56 12.99 1.28 1.16 2.32 8.05
Percentage Error

Table 8
The Calculated waste heat boiler effluents after kinetic parameters optimization in comparison to measured plant data

H2 N2 CO CO2 H2S COS SO2 H2O S2

Test1 Experimental 5.52 132.83 1.95 6.40 13.97 1.27 5.72 96.22 31.62
Calculated 5.84 132.59 2.05 6.43 14.51 1.16 5.67 95.30 31.42
Test2 Experimental 3.87 147.81 1.30 6.04 11.40 0.91 4.45 85.23 27.90
Calculated 6.00 144.37 1.62 5.88 11.60 0.74 4.30 82.78 27.77
Test3 Experimental 2.85 84.78 0.90 4.79 6.66 0.67 2.45 46.27 21.01
Calculated 2.87 87.62 0.99 4.80 7.36 0.57 3.28 45.60 20.30
Test4 Experimental 3.69 93.58 1.37 6.34 11.12 1.12 4.59 62.39 27.69
Calculated 3.69 91.42 1.48 6.34 11.91 1.01 4.11 61.47 27.57
Test5 Experimental 6.31 112.47 2.49 6.59 14.39 1.66 5.71 123.45 38.31
Calculated 5.22 111.75 2.44 6.60 17.48 1.68 6.17 121.4 36.50
Mean Absolute percentage 15.73 1.76 9.88 0.7 8.96 10.57 11.33 1.68 1.93
Error

4. Results and discussions 4.1. Increasing NH3 and O2 molar flow rates

After modeling the reaction furnace and waste heat boiler as the
front end of Claus unit, the influence of different operating condi-
tions were studied on reaction furnace outlet temperature,
hydrogen and carbonyl sulfide production, sulfur conversion effi-
ciency percentage and H2S to SO2 flow ratio. The NH3 and O2 molar
flow rates, and air to acid gas ratio, were some of these operating
conditions that were later allocated much attention in our research
owing to the following optimization work.
The effects of increasing NH3 and O2 molar flow rates in reaction
furnace feed were investigated on reaction furnace temperature, H2
and COS molar flow rate, H2S to SO2 ratio and sulfur conversion
efficiency percentage. Accordingly, the inlet NH3 and O2 molar flow
rates varied from 0 to 20 mol/sec for base test 3 which is only made
of acid gas and air. To put it in another way, sour water gas stripper
and oxygen enrichment flows were not considered in this study.
Fig. 1 shows the effect of increasing O2 and NH3 molar flow rate
on reaction furnace temperature. As seen, increasing the O2 flow
rate increases the furnace temperature which is favorable for
 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757 753

Table 9
The Calculated waste heat boiler effluents after kinetic parameters optimization in comparison to measured plant data using series modeling

H2 N2 CO CO2 H2S COS SO2 H2O S2

Test1 Experimental 5.52 132.83 1.95 6.40 13.97 1.27 5.72 96.22 31.62
Calculated 5.45 134.41 1.96 7.51 15.15 1.11 4.88 95.65 31.73
Test2 Experimental 3.87 147.81 1.30 6.04 11.40 0.91 4.45 85.23 27.90
Calculated 4.74 149.45 1.37 6.89 11.84 0.68 4.30 83.92 27.64
Test3 Experimental 2.85 84.78 0.90 4.79 6.66 0.67 2.45 46.27 21.01
Calculated 2.40 85.99 0.84 5.19 8.02 0.55 2.32 45.62 20.51
Test4 Experimental 3.69 93.58 1.37 6.34 11.12 1.12 4.59 62.39 27.69
Calculated 3.31 94.87 1.46 6.79 11.17 1.02 3.59 63.15 28.30
Test5 Experimental 6.31 112.47 2.49 6.59 14.39 1.66 5.71 123.45 38.31
Calculated 6.34 113.88 2.75 7.76 20.38 1.77 6.74 119.11 34.80
Mean Absolute Percentage 10.05 1.27 5.89 12.92 14.94 14.19 12.59 1.65 3.01
Error

Fig. 1. Effect of increasing NH3 and O2 molar flow rate on reaction furnace
temperature. Fig. 2. Effect of increasing NH3 and O2 molar flow rate on H2 production at reaction
furnace and waste heat boiler effluents.

reactions such as hydrogen sulfide decomposition reaction, Claus

reaction and the following reaction occurring at high temperatures
in the reaction furnace (Karan et al., 1999a):
CO þ H2S 4 COS þ H2
Unlike O2, increasing NH3 molar flow decreases reaction furnace
temperature due to the endothermic nature of NH3 decomposition
reaction. Ammonia utilizes reaction furnace heat reaction as the
required energy for its decomposition and hydrogen production.
Therefore, it is expected that hydrogen molar flow rate increases
with ammonia molar flow rate because of ammonia pyrolysis. Fig. 2
indicates the accuracy of this statement on the hydrogen produc-
tion both in the reaction furnace and waste heat boiler effluents. In
this figure, hydrogen content at the waste heat boiler outlet is less
than the reaction furnace effluents which shows that some
hydrogen molecules were consumed due to hydrogen sulfide
recombination reaction at the waste heat boiler. At higher NH3
molar flow rates (>12 mol/sec), hydrogen contents at the reaction
furnace coincide with those at waste heat boiler resulting from
quenching H2S pyrolysis and combination reactions so that no
decomposition and recombination reactions occur at this low
temperature (Karan et al., 1999c).
Fig. 2 also shows the effect of increasing O2 molar flow rate on
hydrogen content. As seen, the diagram of hydrogen generation has
an increasing trend due to higher temperatures favorable for
hydrogen sulfide decomposition reaction in reaction furnace.
Lower contents of hydrogen at the waste heat boiler effluent in
(16) comparison to the reaction furnace results from favorable hydrogen
sulfide decomposition reaction.
Fig. 3 shows that sulfur conversion efficiency percentage curve
versus NH3 molar flow rate has a minimum at 16 mol/sec after that
its value increases with the increase in NH3 molar flow rate. Fig. 4
also indicates that SO2 molar flow reaches to a minimum at about
16 mol/sec NH3 flow rate while H2S content is maximum at that
point. It is concluded that H2S/SO2 ratio increases then decreases
with increasing NH3 molar flow rate.
Reducing reaction furnace temperature leads to lower H2S
decomposition reaction producing lower sulfur elements and
maintaining the higher content of H2S compound in the system.
The higher H2S content consumes the generated SO2 in the system.
As a result, H2S to SO2 molar flow ratio increased with temperature
and reached its maximum with the increase in NH3 molar flow rate;
the ratio then plummeted due to quenching the forward second
Claus reaction favorable at high temperatures in the reaction
furnace (Monnery et al., 2000).
As hydrogen content increases with increasing O2 molar flow
rate, it is expected that the same trend be observed for sulfur as a
result of hydrogen sulfide decomposition; Fig. 3, however, shows
754 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757

shown in Fig. 5. With the decrease in H2S to SO2 ratio at higher

oxygen contents and more hydrogen sulfide consumption, lower
extent of the second Claus reaction occurs because of the conver-
sion of H2S to SO2. This verifies the observed trend for sulfur in
Fig. 3.
Fig. 6 illustrates the effect of increasing NH3 molar flow rate on
COS production in the reaction furnace and waste heat boiler. This
curve has a maximum which results from competitions among COS
recombination and decomposition reactions and the reaction of
Equation (16) occurring at high temperatures in the reaction
furnace (Karan et al., 1999a).
At lower temperatures in the waste heat boiler, COS combina-
tion reaction overcame decomposition reaction. Increasing reaction
furnace temperature fastens decomposition reaction and reaction
in accordance with Equation (16), resulting in higher carbonyl
sulfide production. At higher oxygen flow rates, on the other hand,
a decreasing trend can be seen in carbonyl sulfide diagram due to
lower hydrogen sulfide content. As seen in Fig. 6, at lower tem-
peratures in the waste heat boiler, higher amounts of carbonyl
sulfide are produced due to the competition between COS
decomposition and recombination reactions.

Fig. 3. Effect of NH3 and O2 inlet molar flow rates on Sulfur conversion efficiency in 4.2. Air to acid gas flow ratio
reaction furnace and waste heat boiler outlet.

Fig. 7 shows the effect of air to acid gas ratio on the reaction
furnace temperature. The air to acid gas flow ratio ranged from 0.4
to 3, but the summation of these two flows was assumed constant.
According to Fig. 7, increasing the air to acid gas ratio results in the
increment of reaction furnace outlet temperature and the order of
arrangement depends on feed composition including H2S, NH3 and
O2 contents. Based on previous statements about influences of
increasing O2 and NH3 molar flow rate, higher temperatures are
expected for feeds including oxygen enrichment flow, and for feeds
including sour water gas stripper, lower temperatures are expected.
In this study, test 2 with sour water gas stripper was lower than
base test 3, and test 4 including oxygen enrichment flow had higher
reaction furnace temperature in comparison to tests 2 and 3. To
complete hydrogen sulfide combustion, increasing the air to acid
gas ratio outfits is indispensable. The combustion produces high

Fig. 4. Effect of NH3 molar flow rate on H2S and SO2 molar flow rates at reaction
furnace outlet.

the opposite trend. It is concluded that the second Claus reaction is

the main source of sulfur production.
By increasing O2 molar flow rate and subsequent temperature
increase in reaction furnace, the H2S decomposition reaction rate
increases and hydrogen sulfide content decreased. Meanwhile, it is
concluded that more O2 diminishes hydrogen sulfide and other
impurity in reaction furnace feed until its complete depletion,
hence the fact that more sulfur dioxide is produced and more
hydrogen sulfide has the chance to take part based on decompo-
sition reaction and hydrogen production reaction due to higher
temperatures favorable for decomposition reactions. Thus, the di-
agram of H2S to SO2 flow ratio has a decreasing trend as has been Fig. 5. Effect of oxygen molar flow on H2S to SO2 ratio.
 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757 755

Fig. 8. Effect of air to acid gas flow ratio on sulfur conversion efficiency at reaction
Fig. 6. Effect of NH3 and O2 molar flow rates on COS molar flow.
furnace outlet.

5. Optimization

The air to acid gas flow ratio, initial feed temperature, and steam
pressure in the WHB are operating variables that can be changed in
operating Claus furnace in order to maintain H2S/SO2 ratio at 2,
minimize COS emissions and maximize sulfur conversion efficiency
at the waste heat boiler output; such variables can be applied in
maximizing reaction furnace temperature as well. Their variation
ranges are determined in accordance with 0.5e3 for the air to acid
gas flow ratio, 75e375  C for the reaction furnace feed temperature
and 5e30 bar for the steam pressure of waste heat boiler. In present
work, one optimization study was performed where objective
functions including COS emission, H2S to SO2 ratio, reaction furnace
temperature and sulfur production were optimized using reaction
furnace feed temperature, air to acid gas ratio and steam pressure.
Tables 10 and 11 report the results of optimization for all tests, i.e.
the values of decision variables and objective function at optimized
condition. Application of new optimized parameters to the series
model showed that the sulfur production did not increase and
these new conditions had no significant effect on its production
from the thermal stage; but instead the H2S to SO2 ratio, and re-
action furnace temperature access to their optimum values. Opti-
Fig. 7. Effect of air to acid gas flow ratio on reaction furnace outlet temperature.
mum conditions do not change carbonyl sulfide emissions from the
waste heat boiler except for tests 1 and 5 with oxygen enrichment
temperature favorable for decomposition reaction of hydrogen and sour water gas stripper streams where improvements in COS
sulfide and carbonyl sulfide; hydrogen sulfide concentration, emissions were observed.
however, decreases at the same time, resulting in lower decom-
position reaction and sulfur production due to lower decomposi-
tion reaction. Fig. 8 shows sulfur conversion efficiency percentage
as a function of the air to acid gas ratio where it primarily increases
with the air to acid gas ratio, reaches its maximum, then assumes
decreasing trend. Place where maximum is observed for feed Table 10
Optimum parameters for Ultramar reaction furnace
including oxygen enrichment stream happens at lower air to acid
gas flow ratio while for feed including sour water gas stripper oc- Air to Acid Gas Ratio Feed Temperature (K) Steam Pressure (bar)
curs at higher air to acid gas flow ratio. Test1 2.30 470.65 10.6
Test2 2.96 579.75 13.4
Test3 2.02 633.86 16.3
Test4 1.60 565.86 20.1
Test5 1.70 411.40 8.5
756 S. Zarei et al. / Journal of Natural Gas Science and Engineering 31 (2016) 747e757

Table 11
Values of objective function at optimum condition.

Optimized Value Initial Value

abs (H2S/SO2-2) 1/TRF (1/K) COS(mol/sec) 1/S2 (sec/mol) abs (H2S/SO2-2) 1/TRF (1/K) COS(mol/sec) 1/S2 (sec/mol)

Test1 0.000690 0.000573 0.287481 0.121963 1.102793 0.000578 0.308213 0.11344

Test2 0.000168 0.000573 0.216893 0.138213 0.751908 0.000608 0.189238 0.130252
Test3 0.005348 0.000598 0.150432 0.183771 1.449303 0.000629 0.153613 0.175517
Test4 0.000499 0.000567 0.285975 0.133987 1.115007 0.000593 0.282918 0.12721
Test5 0.005278 0.000510 0.409502 0.109020 1.025081 0.000534 0.491797 0.103436

6. Conclusions
In this work, a suitable reaction scheme was found to model the
reaction furnace and waste heat boiler of Claus process. In this
modeling, we employed different reactor networks including CSTR
and PFR with optimized kinetic parameters of selected reaction
scheme which reduced the mean percentage error to 7.62%. Fitting
procedure was regulated in a way that the results of kinetic model
match with the experimental reaction furnace and waste heat
boiler effluents. In other words, the developed model can predict
both reaction furnace and waste heat boiler effluents. So as to
survey the effect of oxygen enrichment and sour water gas stripper
(containing ammonia) on the performance of Claus reaction
furnace, different case studies were performed through changing
the oxygen and ammonia molar flow rates. Results indicated that
higher levels of oxygen resulted in higher reaction furnace tem-
peratures, while the presence of ammonia reduced the reaction
furnace temperature. The influence of ammonia and oxygen in-
crements on sulfur conversion is similar, causing sulfur conversion
reduction. An optimization study was conducted to investigate the
optimum operating condition of the reaction furnace and waste
heat boiler including reaction furnace operating temperature,
maximizing sulfur production, minimizing COS emissions and
maintaining H2S/SO2 ratio at constant 2 from the waste heat boiler.
In this optimization, reaction furnace feed temperature, steam
pressure and air to acid gas flow ratio parameters were used.
Nomenclatures
A Cross-sectional area (m2)
h Enthalpy (J/mol)
r rate (mol-sec-m)
C Concentration (mol/m3)
F Molar Flow (mol/sec)
nC Number of components
nR Number of reactions
P Pressure (Pa)
R Gas constant (8.314 J/mol K)
tR Actual mean residence time(sec)
T Temperature (K)
nij Stoichiometric coefficient of component j in reaction i
Subscripts
i Reaction number
j Component number
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